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Ni/Co bimetallic organic frameworks nanospheres for highperformance electrochemical energy storage

Nano Research 2024年第6期17卷 5122-5130页

作者： Jianru Guan Minlu Liu Limin Zhu Jiamei Wang Qing Han Xiaoxia Yang Weibo Hua Lingling Xie Xiaoyu Cao School of Chemistry and Chemical Engineering Key Laboratory of High Specific Energy Materials for Electrochemical Power Sources of Zhengzhou CityHenan University of TechnologyZhengzhou 450001China School of Chemical Engineering and Technology Xi’an Jiaotong UniversityXi’an 710049China School of Environmental Engineering Henan University of TechnologyZhengzhou 450001China

In addition to their many well-known advantages(e.g.,ultra-high porosity,good pore size distribution,easy functionalization,and structural tolerability),metal-organic frameworks(MOFs)are a new class of advanced functional ***,their backbones are highly susceptible to deformation after exposure to acidic or alkaline *** a result of lithium-ion batteries embedding or detaching directly from MOFs,they irreversibly *** a result,they fail to maintain their electrochemical *** factors have hindered the development of MOFs as direct electrode materials,making the design of MOF materials with controlled morphology and stable dimensions a new *** this study,we adopted a versatile and effective method to synthesize a novel MOF material(NiCo-BP(BP=BTC/phen and BTC=1,3,5-benzenetricarboxylic acid))using the rigid ligands 1,10-phenanthroline and homobenzotrizoic acid,and the emergence of the Ni-O/N and Co-O/N coordination layers was observed by extended X-ray absorption fine structure(EXAFS)tests,indicating that Ni and Co were coordinated with heterocyclic N-given atoms to form a stable p-πconjugated ***,the metal-ion is attached to the carboxylic acid ligand on the other side,making the metal-organic skeleton complete and *** nanosphere structure of NiCo-BP(~400 nm)allows for full exposure and utilisation of the active sites,especially the Ni,Co,and phenanthroline units,and exhibit impressively high specific capacity and cycling *** a high current density of 1.0 A·g^(−1),a high discharge specific capacity of 631.6 mAh·g^(−1)was obtained after 1000 *** co-participation of two organic ligands in the coordination is in accordance with the theory of soft and hard acids and bases,which contributes to the ability of the material to maintain a high capacity in cycling as well as its cyclic stability.

关键词： lithium-ion batteries metal organic frame electrochemical energy storage dual ligand hard-soft-acid-base

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Solvation Engineering via Fluorosurfactant Additive Toward Boosted Lithium-Ion Thermoelectrochemical Cells

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Nano-Micro Letters 2024年第4期16卷 253-268页

作者： Yinghong Xu Zhiwei Li Langyuan Wu Hui Dou Xiaogang Zhang Jiangsu Key laboratory of electrochemical energy Storage Technologies College of Material Science and TechnologyNanjing University of Aeronautics and AstronauticsNanjing 211106People’s Republic of China

Lithium-ion thermoelectrochemical cell(LTEC), featuring simultaneous energy conversion and storage, has emerged as promising candidate for low-grade heat harvesting. However, relatively poor thermosensitivity and heat-to-current behavior limit the application of LTECs using LiPF_6 electrolyte. Introducing additives into bulk electrolyte is a reasonable strategy to solve such problem by modifying the solvation structure of electrolyte ions. In this work, we develop a dual-salt electrolyte with fluorosurfactant(FS) additive to achieve high thermopower and durability of LTECs during the conversion of low-grade heat into electricity. The addition of FS induces a unique Li~+ solvation with the aggregated double anions through a crowded electrolyte environment,resulting in an enhanced mobility kinetics of Li~+ as well as boosted thermoelectrochemical performances. By coupling optimized electrolyte with graphite electrode, a high thermopower of 13.8 mV K^(-1) and a normalized output power density of 3.99 mW m^(–2) K^(–2) as well as an outstanding output energy density of 607.96 J m^(-2) can be *** results demonstrate that the optimization of electrolyte by regulating solvation structure will inject new vitality into the construction of thermoelectrochemical devices with attractive properties.

关键词： Solvation engineering Fluorosurfactant Ionic thermoelectric Lithium-ion thermoelectrochemical cell Low-grade heat

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Dual-filler reinforced PVDF-HFP based polymer electrolyte enabling high-safety design of lithium metal batteries

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Nano Research 2024年第6期17卷 5251-5260页

作者： Chang Fang Kangsheng Huang Jing Zhao Shiqi Tian Hui Dou Xiaogang Zhang Jiangsu Key laboratory of electrochemical energy Storage Technologies College of Materials Science and TechnologyNanjing University of Aeronautics and AstronauticsNanjing 210016China

Despite the high energy density of lithium metal batteries(LMBs),their application in rechargeable batteries is still hampered due to insufficient ***,we present a novel flame-retardant solid-state electrolyte based on polyvinylidene fluoride-hexafluoropropylene(PVDF-HFP)with nano SiO_(2)aerogel as an inert filler but Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)as an auxiliary component to enhance the ion *** introduction of SiO_(2)aerogels imparts the polymer electrolyte with exceptional thermal stability and flame ***,the interaction between hydroxyl groups of SiO_(2)particles and PVDF-HFP creates a strong cross-linking structure,enhancing the mechanical strength and stability of the ***,the presence of SiO_(2)aerogel and LLZTO facilitates the dissociation of lithium salts through Lewis acid-base interactions,resulting in a high ionic conductivity of 1.01×10^(−3)S·cm^(−1)and a wide electrochemical window of~5.0 V at room temperature for the prepared ***,the assembled Li|Li cell demonstrates the excellent resistance to lithium dendrite and runs stablly for over 1500 h at a current density of 0.25 mA·cm^(−2).Thus,we prepare a pouch cell with high safety,which can work normally after short-circuiting under the external folding and cutting.

关键词： polymer electrolyte SiO_(2)/Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)dual-filler non-flammable long cycle life lithium metal battery

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Sulfur doped iron-nitrogen-hard carbon nanosheets as efficient and robust noble metal-free catalysts for oxygen reduction reaction in PEMFC

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Journal of energy Chemistry 2024年第2期89卷 422-433,I0010页

作者： Bin Liu Jiawang Li Bowen Yan Qi Wei Xingyu Wen Huarui Xie Huan He Pei Kang Shen Zhi Qun Tian Collaborative Innovation Center of Sustainable energy Materials School of Physical Science and TechnologyGuangxi UniversityGuangxi Key Laboratory of Electrochemical Energy MaterialsState Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite StructuresNanning 530004GuangxiChina

Transition metal-nitrogen-carbon(M-N-C)as a promising substitute for the conventional noble metalbased catalyst still suffers from low activity and durability for oxygen reduction reaction(ORR)in proton exchange membrane fuel cells(PEMFCs).To tackle the issue,herein,a new type of sulfur-doped ironnitrogen-hard carbon(S-Fe-N-HC)nanosheets with high activity and durability in acid media were developed by using a newly synthesized precursor of amide-based polymer with Fe ions based on copolymerizing two monomers of 2,5-thiophene dicarboxylic acid(TDA)as S source and 1,8-diaminonaphthalene(DAN)as N source via an amination *** as-synthesized S-Fe-N-HC features highly dispersed atomic Fe Nxmoieties embedded into rich thiophene-S doped hard carbon nanosheets filled with highly twisted graphite-like microcrystals,which is distinguished from the majority of M-N-C with soft or graphitic carbon *** unique characteristics endow S-Fe-N-HC with high ORR activity and outstanding durability in 0.5 M H_(2)SO_(4).Its initial half-wave potential is 0.80 V and the corresponding loss is only 21 m V after 30,000 ***,its practical PEMFC performance is a maximum power output of 628.0 mW cm^(-2)and a slight power density loss is 83.0 m W cm^(-2)after 200-cycle practical ***,theoretical calculation shows that the activity of Fe Nxmoieties on ORR can be further enhanced by sulfur doping at meta-site near FeN_(4)*** results evidently demonstrate that the dual effect of hard carbon substrate and S doping derived from the precursor platform of amid-polymers can effectively enhance the activity and durability of Fe-N-C catalysts,providing a new guidance for developing advanced M-N-C catalysts for ORR.

关键词： Transition metal-nitrogen-carbon Oxygen reduction reaction Hard carbon Amide based polymer reaction Proton exchange membrane cells

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Bifunctional interstitial phosphorous doping strategy boosts platinum-zinc alloy for efficient ammonia oxidation reaction and hydrogen evolution reaction

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Nano Research 2024年第3期17卷 1182-1189页

作者： Tianqi Yu Kexin Tan Jia Wu Yongjin Zou Shibin Yin Guangxi Key laboratory of electrochemical energy Materials School of Chemistry and Chemical EngineeringGuangxi UniversityNanning 530004China Guangxi Key laboratory of Information Materials Guilin University of Electronic TechnologyGuilin 541004China

It is still a lack of bifunctional catalysts for ammonia oxidation reaction(AOR)and hydrogen evolution reaction(HER)due to their different reaction *** this work,P is doped into PtZn alloy by calcination with NaH_(2)PO_(2) as P source to induce the lattice tensile strain of Pt and the electronic interaction between P and Zn,which optimizes the AOR and HER activity *** sample with the optimal P content can drive the AOR peak current density of 293.6 mA·mgPt^(-1),which is almost 2.7 times of *** HER,the overpotential at^(-1)0 mA·cm^(-2) is only 23 mV with Tafel slope of 34.1 mV·dec^(-1).Furthermore,only 0.59 V is needed to obtain 50 mA·mgPt^(-1) for ammonia electrolysis under a two-electrode ***,this work shows an ingenious method to design bifunctional catalysts for ammonia electrolysis.

关键词： PtZn alloy phosphorous doping ammonia oxidation reaction hydrogen evolution reaction bifunctional catalyst

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Activatable photoacoustic bioprobe for visual detection of aging in vivo

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Chinese Chemical Letters 2024年第4期35卷 324-329页

作者： Zihong Li Jie Cheng Ping Huang Guoliang Wu Weiying Lin Institute of Optical Materials and Chemical Biology Guangxi Key Laboratory of Electrochemical Energy MaterialsSchool of Chemistry and Chemical EngineeringGuangxi UniversityNanning 530004China

Aging is a natural physiological process with various challenges, related to the loss of homeostasis within the organism, which is not a disease, but a significantly strong risk factor for multiple diseases, including myocardial infarction, stroke, some age-related cancers, macular degeneration, osteoarthritis, neurodegeneration, and many others. In the body, the main manifestation of aging is cellular aging, which exists within tissues and has a local or global impact on tissue function. However, the lack of effective aging detection tools has always been an issue that cannot be ignored in the field of aging research. Therefore,it is necessary to construct a non-invasive tool for in vivo detection of aging. Here, we show that the photoacoustic probe(LGAL), which has peak excitation and emission wavelengths in the near-infrared optical window, binds in vivo and at high contrast to the hallmark of aging, and allows for the microscopic imaging of aging through the intact mice. Firstly, this tool LGAL has been successfully applied to detect senescence in cells, displaying stronger photoacoustic signals than normal cells. Then, by using the photoacoustic probe, the blood vessels and tissues inside the mice can be visualized. Young and elderly mice exhibit varying intensities of photoacoustic signals, marking the first time a probe has been used to explore the aging of blood vessels and tissues inside the mice. Finally, we monitored the changes in the degree of aging during tumor treatment under photoacoustic(PA) imaging for the first time. As the treatment time increased, the degree of aging of the tumor gradually deepened. We expect the powerful tool could be a noninvasive and powerful tool for the study of aging biology.

关键词： Near-infrared Photoacoustic Aging Senescence Tumor Sa-β-gal

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Evaluating the tumor stratification with a lysosomal pH sensitive-probe by fluorescence lifetime imaging

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Chinese Chemical Letters 2024年第3期35卷 262-267页

作者： Jun Yan Xing Liang Qian Zhang Luolin Wang Weiying Lin Guangxi Key laboratory of electrochemical energy Materials Institute of Optical Materials and Chemical BiologySchool of Chemistry and Chemical EngineeringGuangxi UniversityNanning 530004China

Owing to the anaerobic metabolism in the tumor,abundant acidic metabolites are produced and accumulated in the ***,the cells in different tumor layers are directly linked to the pH ***,due to the lack of robust tools,the high-efficient evaluation of the acidic micro-environment of tumor stratification faces the challenge of accurate *** designed a new pH sensitive fluorescent lifetime probe target to *** we expected,the fluorescence lifetime of PLN possesses a good linear fit to the pH value,which could detect the pH change at a single lysosome level in real time,and then evaluate the different acidity of tumor *** probe PLN is successfully used to evaluate the tumor stratification by fluorescence lifetime imaging microscopy(FLIM)for the first time,which is of great significance in the preoperative diagnosis of clinical tumor treatment or evaluation of drug delivery effect.

关键词： FLIM pH Fluorescence imaging Lysosome Tumor imaging

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Solid-state synthesis and ion transport characteristics of the β-KSbF_(4) for all-solid-state fluoride-ion batteries

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Journal of energy Chemistry 2024年第7期94卷 758-767页

作者： Jiali Liu Huahui Zhao Jingcheng Xia Lingguang Yi Xiaoyi Chen Dongdu Li Shuhan Ni Xinyi Su Yixuan Chen Min Liu Xianyou Wang National Base for International Science&Technology Cooperation National Local Joint Engineering Laboratory for Key Materials of New Energy Storage BatteryHunan Province Key Laboratory of Electrochemical Energy Storage&ConversionSchool of ChemistryXiangtan UniversityXiangtan 411105HunanChina College of New energy Ningbo University of TechnologyNingbo 315336ZhejiangChina

All-solid-state fluoride ion batteries(FIBs)have been recently considered as a post-lithium-ion battery system due to their high safety and high energy *** like all solid-state lithium batteries,the key to the development of FIBs lies in room-temperature electrolytes with high ionic conductivity.β-KSbF_(4) is a kind of promising solid-state electrolyte for FIBs owing to its rational ionic conductivity and relatively wide electrochemical stability window at room ***,the previous synthesis routes ofβ-KSbF_(4) required the use of highly toxic hydrofluoric acid and the ionic conductivity of as-prepared product needs to be further ***,the β-KSbF_(4) sample with an ionic conductivity of 1.04×10^(-4)s cm^(-1)(30°C)is synthesized through the simple solid-state *** order to account for the high ionic conductivity of the as-synthesizedβ-KSbF_(4),X-ray diffraction(XRD),scanning electron microscopy(SEM),and energy dispersive X-ray spectroscopy(EDS)are used to characterize the physic-ochemical *** results show that the as-synthesizedβ-KSbF_(4) exhibits higher carrier concentra-tion of 1.0×10^(-6)S cm-Hz^(-1)K and hopping frequency of 1.31×10^(6)Hz at 30°C due to the formation of the fluorine ***,the hopping frequency shows the same trend as the changes of ionic conductivity with the changes of temperature,while the carrier concentration is found to be almost *** two different trends indicate the hopping frequency is mainly responsible for the ionic conduc-tion behavior withinβ-KSbF_(4).Furthermore,the all-solid-state FIBs,in which Ag and Pb+PbF_(2) are adopted as cathode and anode,andβ-KSbF_(4) as fluoride ion conductor,are capable of reversible charge and *** assembled FIBs show a discharge capacity of 108.4 mA h g^(-1) at 1st cycle and 74.2 mA h g^(-1) at 50th *** on an examination of the capacity decay mechanism,it has been found that deterioration of the electrolyte/electrode int

关键词： Solid-state electrolyte Carrier concentration Hopping frequency β-KSbF_(4) All-solid-state fluoride ion batteries

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Special issue on electrochemical conversion and utilization of hydrogen energy

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Frontiers in energy 2024年第3期18卷 263-264页

作者： Yun ZHENG Bo YU Xiaogang FU Jiujun ZHANG Institute of New energy Materials and Engineering School of Materials Science and EngineeringFuzhou UniversityFuzhou 350108China State Key laboratory of Solidification Processing Atomic Control&Catalysis Engineering LaboratorySchool of Materials Science and EngineeringNorthwestern Polytechnical UniversityXi’an 710072China Institute of Nuclear and New energy Technology Tsinghua UniversityBeijing 100084China

The concerns over energy crisis and climate change caused by the excessive consumption of fossil fuels and the associated emission of greenhouse gases, have driven many countries to develop policies for an energy transition into zero-carbon energy sources, essentially aiming at decarbonizing their energy systems. Among various renewable sources, hydrogen has been hailed as an ideal alternative to provide secure, cost-effective, and non-polluting energy. In recent years, there has been noteworthy progress in hydrogen electrochemical conversion and utilization techniques and devices, including water electrolyzers, proton-exchange membrane fuel cells (PEMFCs), solid oxide fuel cells (SOFCs), etc. Each of these technologies has yielded a series of encouraging advances. To showcase these recent advances, Frontiers in energy is launching a special issue titled “electrochemical conversion and utilization of hydrogen energy”.

关键词： hydrogen energy. electrochemical

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Model reduction of fractional impedance spectra for time–frequency analysis of batteries, fuel cells, and supercapacitors

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Carbon energy 2024年第1期6卷 108-141页

作者： Weiheng Li Qiu-An Huang Yuxuan Bai Jia Wang Linlin Wang Yuyu Liu Yufeng Zhao Xifei Li Jiujun Zhang Institute for Sustainable energy/College of Sciences Shanghai UniversityShanghaiChina Shanxi Key laboratory of Nanomaterials and Nanotechnology School of Mechanical and Electrical EngineeringXi'an University of Architecture and TechnologyXi'anShaanxiChina Xi'an Key laboratory of New energy Materials and Devices School of Materials Science and EngineeringInstitute of Advanced Electrochemical EnergyXi'an University of TechnologyXi'anShaanxiChina

Joint time–frequency analysis is an emerging method for interpreting the underlying physics in fuel cells,batteries,and *** increase the reliability of time–frequency analysis,a theoretical correlation between frequency-domain stationary analysis and time-domain transient analysis is urgently *** present work formularizes a thorough model reduction of fractional impedance spectra for electrochemical energy devices involving not only the model reduction from fractional-order models to integer-order models and from high-to low-order RC circuits but also insight into the evolution of the characteristic time constants during the whole reduction *** following work has been carried out:(i)the model-reduction theory is addressed for typical Warburg elements and RC circuits based on the continued fraction expansion theory and the response error minimization technique,respectively;(ii)the order effect on the model reduction of typical Warburg elements is quantitatively evaluated by time–frequency analysis;(iii)the results of time–frequency analysis are confirmed to be useful to determine the reduction order in terms of the kinetic information needed to be captured;and(iv)the results of time–frequency analysis are validated for the model reduction of fractional impedance spectra for lithium-ion batteries,supercapacitors,and solid oxide fuel *** turn,the numerical validation has demonstrated the powerful function of the joint time–frequency *** thorough model reduction of fractional impedance spectra addressed in the present work not only clarifies the relationship between time-domain transient analysis and frequency-domain stationary analysis but also enhances the reliability of the joint time–frequency analysis for electrochemical energy devices.

关键词： battery,fuel cell,supercapacitor fractional impedance spectroscopy model reduction time-frequency analysis

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